Distorted commo-Cobaltacarboranes Based on the 5,6-Dicarba-nido-decaborane(12): The First Bimetal Cobalt-Copper Zwitterion-Containing Cluster with Four (B-H)···Cu Bonds Not Showing Fluxional Behavior in Solution.

Treatment of a recently reported complex [PhP][closo,nido-CoH(2,4-CBH)(7,8-CBH)] (1) either by HO in acetone or NaH in THF leads to the loss of both the bridging and terminal hydrides yielding the diamagnetic salt of an anionic commo-cobaltacarborane [PhP][Co(2,4-isonido-CBH)] (2) with the {CoCB}-cluster units adopting a distorted skeletal geometry of the isonido-type. The anionic commo complex 2 reacts with in situ generated cationic [CuPPh] species to give stable copper-cobalt zwitterion [PhPCu][Co(2,4-isonido-CBH)] (3) with four two-electron, three-center (B-H)···Cu bonds, and exhibits no fluxional behavior in solution. Complex 3, at the same time, in CHCl in the presence of 2-fold excess of PPh readily converts to a new anionic species [(PhP)Cu][Co(2,4-isonido-CBH)] (4) which retains initial isonido geometry.

An unusual conversion of paramagnetic [3-Cl-3,3,8-{Ph2P(CH2)nPPh-µ-(C6H4-ortho)}-1,2-(CH3)2-closo-3,1,2-RuIIIC2B9H8] (n=3 and 4) to form the first 18-electron P-phenylene ortho-cycloboronated closo-ruthenacarboranes with a dioxygen ligand.

Treatment of [3-Cl-3,3,8-[Ph2P(CH2)nPPh-µ-(C6H4-ortho)]-1,2-Me2-closo-3,1,2-RuIIIC2B9H8] (1, n=3; 2, n=4) with an excess of KOH in a 1:1 benzene/methanol mixture at room temperature in air affords new dioxygen closo-ruthenacarborane complexes [3-(η2-O2)-3,3,8-[Ph2P(CH2)nPPh-µ-(C6H4-ortho)]-1,2-Me2-closo-3,1,2-RuIIIC2B9H8] (3, n=3) and (4, n=4) in 42.5% and 45.8% yield respectively.

Frequency distributions of 90Sr and 137Cs concentrations in an ecosystem of the "Red Forest" area in the Chernobyl exclusion zone.

In the most highly contaminated region of the Chernobyl Exclusion Zone, the "Red Forest" site, the accumulation of the major dose-affecting radionuclides (90Sr and 137Cs) within the components of an ecological system encompassing 3,000 m(2) was characterized. The sampled components included soils (top 0-10 cm depth), Molina caerulea (blue moor grass), Camponotus vagus (carpenter ants), and Pelobates fuscus (spade-footed toad). In a comparison among the components of this ecosystem, the 90Sr and 137Cs concentrations measured in 40 separate grids exhibited significant differences, while the frequency distribution of the values was close to a logarithmically-normal leptokurtic distribution with a significant right-side skew.

Carborane complexes of ruthenium(III): studies on thermal reaction chemistry and the catalyst design for atom transfer radical polymerization of methyl methacrylate.

The heating of the 18-electron complex [3,3-(dppb)-3-H-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (3) in benzene at 80 °C in the presence of a small amount of CCl(4) as initiator afforded paramagnetic 17-electron species [3,3-(dppb)-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (4) along with minor amounts of two P-phenylene ortho-cycloboronated derivatives [3-Cl-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (5) and [3,7-Cl(2)-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (6) in total yield of ca. 80%. The heating of either 3 or 4 in toluene at 95 °C in the absence of CCl(4) led to the selective formation of 5, which was isolated in 64% and 46% yield, respectively.

Stable exo-nido-metallacarboranes (M = Os(IV)) that incorporate meta-carborane-based dicarbollide ligands.

Reactions of the [K]+ salts of the [nido-7,9-C2B9H12]- anion (2) and its C-phenylated derivative [7-Ph-nido-7,9-C2B9H11]- (4) with [OsCl2(PPh3)3] (3) proceed in benzene at ambient temperature with the formation of 16-electron chlorohydrido-Os(IV) exo-nido complexes, [exo-nido-10,11-{(Ph3P)2OsHCl}-10,11-(mu-H)2-7-R-7,9-C2B9H8] (5: R = H; 6: R = Ph), along with the small amounts of the charge-compensated nido-carboranes [nido-7,9-C2B9H11PPh3] (7) and [7-Ph-nido-7,9-C2B9H10PPh3] (8) as byproducts. However, when carried out under mild heating in ethanol, the reaction of 2 with 3 selectively afforded a 16-electron dihydrido-Os(IV) exo-nido complex [exo-nido-10,11-{(Ph3P)2OsH2}-10,11-(mu-H)2-7,9-C2B9H9] (9). Structures of both complexes 5 and 9 have been confirmed by single-crystal X-ray diffraction studies, which revealed that nido-carboranes in these species function as a bidentate dicarbollide ligands [7-R-nido-7,9-C2B9H10]2- linked to the Os(IV) center via two B-H.

Synthesis and characterization of novel monocarbollide exo-closo-(pi-arene)biruthenacarboranes [(PPh3)mClRu(eta6-C6H5R)Ru'CB10H11-n(OMe)n] (where R = H, m = 2, n = 1; R = mu-PPh2, m = 1, n = 0, 1).

The monocarbon carborane [Cs][nido-7-CB(10)H(13)] reacts with the 16-electron [RuCl(2)(PPh(3))(3)] in a solution of benzene/methanol in the presence of N,N,N',N'-tetramethylnaphthalene-1,8-diamine as the base to give a series of 12-vertex monocarbon arene-biruthenacarborane complexes of two types: [closo-2-[7,11-exo-RuClPPh(3)(mu,eta(6)-C(6)H(5)PPh(2))]-7,11-(mu-H)(2)-2,1-RuCB(10)H(8)R] (5, R = H; 6, R = 6-MeO; 7, R = 3-MeO) and [closo-2-(eta(6)-C(6)H(6))-10,11,12-[exo-RuCl(PPh(3))(2)]-10,11,12-(mu-H)(3)-2,1-RuCB(10)H(7)R(1)] (8a, R(1) = 6-MeO; 8b, R(1) = 3-MeO, inseparable mixture of isomers) along with trace amounts of 10-vertex mononuclear hypercloso/isocloso-type complexes [2,2-(PPh(3))(2)-2-H-3,9-(MeO)(2)-2,1-RuCB(8)H(7)] (9) and [2,5-(Ph(3)P)-2-Cl-2-H-3,9-(MeO)(2)-2,1-RuCB(8)H(6)] (10). Binuclear ruthenacarborane clusters of both series were characterized by a combination of analytical and multinuclear NMR spectroscopic data and by single-crystal X-ray diffraction studies of three selected complexes, 6-8. In solution, isomers 8a,b have been shown to undergo the isomerization process through the scrambling of the exo-[RuCl(PPh(3))(2)] fragment about two adjacent triangular cage boron faces B(7)B(11)B(12) and B(8)B(9)B(12).

Carboracycles: Macrocyclic Compounds Composed of Carborane Icosahedra Linked by Organic Bridging Groups.

A family of macrocyclic compounds are described, together with their precursors. These cycles are composed of icosahedral carboranes linked via their carbon vertices through 1,3-trimethylene, alpha,alpha'-1,3-xylylene, or alpha,alpha'-2,6-lutidylene groups. The compounds cyclo-(1,3-trimethylene-1',2'-closo-1',2'-C(2)B(10)H(10))(4) (6a), cyclo-(1,3-trimethylene-1',2'-closo-9',12'-dimethyl-1',2'-C(2)B(10)H(8))(4) (6b), cyclo-(1,3-trimethylene-1',2'-closo-1',2'-C(2)B(10)H(10))(3) (9), cyclo-(alpha,alpha'-1,3-xylylene-1',2'-closo-1',2'-C(2)B(10)H(10))(2) (11a), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (11b), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-9',10'-dimethyl-1,7-C(2)B(10)H(8))(2) (11c), cyclo-(alpha,alpha'-1,3-xylylene-1',2'-closo-1',2'-C(2)B(10)H(10))(4) (12), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-1',7'-C(2)B(10)H(10))(3) (13), cyclo-(alpha,alpha'-2,6-lutidylene-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (19), and cyclo-(alpha,alpha'-2,6-lutidylene N-oxide-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (20) have been synthesized.